毛晨岳,赵颂,何鹏鹏,王志,王纪孝

• 1:天津大学 化工学院 化学工程研究所，天津市膜科学与海水淡化技术重点实验室，化学工程联合国家重点实验室(天津大学)，天津 化学化工协同创新中心，天津 300350

摘要(Abstract)：

共价有机框架（COFs）材料是由有机结构单元通过共价键连接形成的多孔纳米材料，具有比表面积大、孔隙率高、结构规整有序、稳定性好的优点，是制备高性能分离膜的理想材料，因而在纳滤膜研究领域引起广泛关注。文章综述了近几年来研究者利用掺杂法、层层组装法、界面聚合法、原位生长法等制备COFs纳滤膜的研究成果，对不同制膜方法的特点进行分析，并指出目前COFs纳滤膜研究中存在的问题，最后对COFs纳滤膜的未来发展前景作出展望。

关键词(KeyWords)： 共价有机框架材料;纳滤;膜;分离;层层组装;界面聚合;原位生长

Abstract:

Keywords:

基金项目(Foundation): 天津市自然科学基金（19JCYBJC20900）。

作者(Author): 毛晨岳,赵颂,何鹏鹏,王志,王纪孝

DOI: 10.3969/j.issn.1003-9015.2021.01.002

参考文献(References)：

• [1] MOHAMMAD A W, TEOW Y H, ANG W L, et al. Nanofiltration membranes review:Recent advances and future prospects[J]. Desalination, 2015, 356:226-254.
  [2] ABDELLAH M H, PEREZ-MANRIQUEZ L, PUSPASARI T, et al. A catechin/cellulose composite membrane for organic solvent nanofiltration[J]. Journal of Membrane Science, 2018, 567:139-145.
  [3] ZHU J Y, YUAN S S, ULIANA A, et al. High-flux thin film composite membranes for nanofiltration mediated by a rapid co-deposition of polydopamine/piperazine[J]. Journal of Membrane Science, 2018, 554:97-108.
  [4] ZHANG Z, KANG G D, YU H J, et al. Fabrication of a highly permeable composite nanofiltration membrane via interfacial polymerization by adding a novel acyl chloride monomer with an anhydride group[J]. Journal of Membrane Science, 2019, 570:403-409.
  [5] VAN GOETHEM C, VERBEKE R, PFANMÖLLER M, et al. The role of MOFs in thin-film nanocomposite (TFN) membranes[J]. Journal of Membrane Science, 2018, 563:938-948.
  [6] WU M Y, MA T Y, SU Y L, et al. Fabrication of composite nanofiltration membrane by incorporating attapulgite nanorods during interfacial polymerization for high water flux and antifouling property[J]. Journal of Membrane Science, 2017, 544:79-87.
  [7] ZHU S, ZHAO S, WANG Z, et al. Improved performance of polyamide thin-film composite nanofiltration membrane by using polyetersulfone/polyaniline membrane as the substrate[J]. Journal of Membrane Science, 2015, 493:263-274.
  [8] 刘春晖, 马晓莉. 共价有机框架材料的最新进展[J]. 化工进展, 2019, 38(11):4978-4990. LIU C H, MA X L. Latest development of covalent organic frameworks[J]. Chemical Industry and Engineering Progress, 2019, 38(11):4978-4990.
  [9] 胡慧, 闫欠欠, 格日乐, 等. 共价有机框架材料在多相催化领域的研究进展[J]. 催化学报, 2018, 39(7):1167-1179. HU H, YAN Q Q, GE R L, et al. Covalent organic frameworks as heterogeneous catalysts[J]. Chinese Journal of Catalysis, 2019, 38(11):4978-4990.
  [10] 李子强, 刘大朋, 何健, 等. 共价有机框架材料在环境保护领域中的应用研究进展[J]. 环境工程, 2019, 37(4):98-103. LI Z Q, LIU D P, HE J, et al. Research progress of covalent organic framework materials in environmental protection[J]. Environmental Engineering, 2019, 37(4):98-103.
  [11] WANG J L, ZHUANG S T. Covalent organic frameworks (COFs) for environmental applications[J]. Coordination Chemistry Reviews, 2019, 400:213046.
  [12] 刘小舟, 王钰杰, 刘耀祖, 等. 一种高比表面积共价有机框架材料的合成及药物缓释性能[J]. 高等学校化学学报, 2019, 40(9):1813-1817. LIU X Z, WANG Y J, LIU Y Z, et al. A covalent organic framework with high surface area for drug delivery[J]. Chemical Journal of Chinese Universities, 2019, 40(9):1813-1817.
  [13] ZENG Y F, ZOU R Q, ZHAO Y L. Covalent organic frameworks for CO₂ capture[J]. Advanced Materials, 2016, 28:2855-2873.
  [14] YUAN S S, LI X, ZHU J Y, et al. Covalent organic frameworks for membrane separation[J]. Chemical Society Review, 2019, 48:2665-2681.
  [15] CÔTÉ A P, BENIN A I, OCKWIG N W, et al. Porous, crystalline, covalent organic frameworks[J]. Science, 2005. 310:1166-1170.
  [16] KUHN P, ANTONIETTI M, THOMAS A. Porous, covalent triazine-based frameworks prepared by ionothermal synthesis[J]. Angewandte Chemie International Edition, 2008, 47(18):3450-3453.
  [17] URIBE-ROMO F J, HUNT J R, FURUKAWA H, et al. A crystalline imine-linked 3D porous covalent organic framework[J]. Journal of the American Chemistry Society. 2009, 131:4570-4571.
  [18] SMITH B J, OVERHOLTS A C, HWANG N, et al. Insight into the crystallization of amorphous imine-linked polymer networks to 2D covalent organic frameworks[J]. Chemical Communications, 2016, 52:3690-3693.
  [19] LI J, ZHOU X, WANG J, et al. Two-dimensional covalent organic frameworks (COFs) for membrane separation:A mini review[J]. Industrial & Engineering Chemistry Research, 2019, 58:15394-15406.
  [20] WANG H, ZENG Z T, XU P, et al. Recent progress in covalent organic framework thin films:Fabrications, applications and perspectives[J]. Chemical Society Review, 2019, 48:488-516.
  [21] 吴梦园. 基于共价有机骨架材料制备超薄复合纳滤膜[D]. 天津:天津大学, 2018. WU M Y. Preparation of ultrathin composite nanofiltration membranes based on covalent organic frameworks[D]. Tianjin:Tianjin University, 2018.
  [22] WU M Y, YUAN J Q, WU H, et al. Ultrathin nanofiltration membrane with polydopamine-covalent organic framework interlayer for enhanced permeability and structural stability[J]. Journal of Membrane Science, 2019, 576:131-141.
  [23] YUAN J Q, WU M Y, WU H, et al. Covalent organic framework-modulated interfacial polymerization for ultrathin desalination membranes[J]. Journal of Materials Chemistry A, 2019, 7:25641-25649.
  [24] ZHANG Z, SHI X S, WANG R, et al. Ultra-permeable polyamide membranes harvested by covalent organic framework nanofiber scaffolds:a two-in-one strategy[J]. Chemical Science, 2019, 10:9077-9083.
  [25] LI C, LI S X, TIAN L, et al. Covalent organic frameworks (COFs)-incorporated thin film nanocomposite (TFN) membranes for high-flux organic solvent nanofiltration (OSN)[J]. Journal of Membrane Science, 2019, 572:520-531.
  [26] XU L N, SHAN B T, GAO C J, et al. Multifunctional thin-film nanocomposite membranes comprising covalent organic nanosheets with high crystallinity for efficient reverse osmosis desalination[J]. Journal of Membrane Science, 2020, 593:117398.
  [27] XU L N, XU J, SHAN B T, et al. TpPa-2-incorporated mixed matrix membranes for efficient water purification[J]. Journal of Membrane Science, 2017, 526:355-366.
  [28] CHANDRA S, KANDAMBETH S, BISWAL B P, et al. Chemically stable multilayered covalent organic nanosheets from covalent organic frameworks via mechanical delamination[J]. Journal of the American Chemistry Society, 2013, 135:17853-17861.
  [29] WANG S, WANG Q Y, SHAO P P, et al. Exfoliation of covalent organic frameworks into few-layer redox active nanosheets as cathode materials for lithium-ion batteries[J]. Journal of the American Chemistry Society, 2017, 139:4258-4261.
  [30] LI G, ZHANG K, TSURU T. Two-dimensional covalent organic framework (COF) membranes fabricated via the assembly of exfoliated COF nanosheets[J]. ACS Applied Materials & Interfaces, 2017, 9:8433-8436.
  [31] KANG Z X, PENG Y W, QIAN Y H, et al. Mixed matrix membranes (MMMs) comprising exfoliated 2D covalent organic frameworks(COFs) for efficient CO₂ separation[J]. Chemistry of Materials, 2016, 28:1277-1285.
  [32] PENG Y W, HUANG Y, ZHU Y H, et al. Ultrathin two-dimensional covalent organic framework nanosheets:Preparation and application in highly sensitive and selective DNA detection[J]. Journal of the American Chemistry Society, 2017, 139:8698-8704.
  [33] MU X W, ZHAN J, WANG Z L, et al. A novel and efficient strategy to exfoliation of covalent organic frameworks and a significant advantage of covalent organic frameworks nanosheets as polymer nano-enhancer:High interface compatibility[J]. Journal of Colloid and Interface Science, 2019, 539:609-618.
  [34] KHAN N A, YUAN J Q, WU H, et al. Mixed nanosheet membranes assembled from chemically grafted graphene oxide and covalent organic frameworks for ultra-high water flux[J]. ACS Applied Materials & Interfaces, 2019, 11:28978−28986.
  [35] BURKE D W, SUN C, CASTANO I, et al. Acid exfoliation of imine-linked covalent organic frameworks enables solution processing into crystalline thin films[J]. Angewandte Chemie International Edition, 2019, 59(13):5165-5171.
  [36] CHEN X D, LI Y S, WANG L, et al. High-lithium-affinity chemically exfoliated 2D covalent organic frameworks[J]. Advanced Materials, 2019, 31:1901640.
  [37] YAO J, LIU C, LIU X Q, et al. Azobenzene-assisted exfoliation of 2D covalent organic frameworks into large-area, few-layer nanosheets for high flux and selective molecular separation membrane[J]. Journal of Membrane Science, 2020, 601:117864.
  [38] MITRA S, KANDAMBETH S, BISWAL B P, et al. Self-exfoliated guanidinium-based ionic covalent organic nanosheets (iCONs)[J]. Journal of the American Chemistry Society, 2016, 138:2823-2828.
  [39] LI Y, ZHANG M C, GUO X H, et al. Growth of high-quality covalent organic framework nanosheets at the interface of two miscible organic solvents[J]. Nanoscale Horizons, 2018, 3:205-212.
  [40] LI G L, WANG W, FANG Q L, et al. Covalent triazine frameworks membrane with highly ordered skeleton nanopores for robust and precise molecule/ion separation[J]. Journal of Membrane Science, 2020, 595:117525.
  [41] SHI X S, MA D W, XU F, et al. Table-salt enabled interface-confined synthesis of covalent organic framework (COF) nanosheets[J]. Chemical Science, 2020, 11:989-996.
  [42] ZHANG W X, ZHANG L M, ZHAO H F, et al. A two-dimensional cationic covalent organic framework membrane for selective molecular sieving[J]. Journal of Materials Chemistry A, 2018, 6:13331-13339.
  [43] 张旭珂. 基于二维杂化材料制备及用于染料/盐分离的高性能复合膜研究[D]. 郑州:郑州大学, 2019. ZHANG X K. Construction of high performance composite membrane based 2D hybrid materials for dye/salt separation[D]. Zhengzhou:Zhengzhou University, 2019.
  [44] KONG G D, PANG J, TANG Y C, et al. Efficient dye nanofiltration of a graphene oxide membrane via combination with a covalent organic framework by hot pressing[J]. Journal of Materials Chemistry A, 2019, 7:24301-24310.
  [45] SHI X S, WANG R, XIAO A K, et al. Layer-by-layer synthesis of covalent organic frameworks on porous substrates for fast molecular separations[J]. ACS Applied Nano Materials, 2018, 1:6320-6326.
  [46] HAO S, JIANG L, LI Y L, et al. Facile preparation of COF composite membranes for nanofiltration by stoichiometric spraying layer-by-layer self-assembly[J]. Chemical Communications, 2020, 56:419-422.
  [47] 应允攀. 面向化工分离的纳米多孔材料复合膜的制备[D]. 北京:北京化工大学, 2017 YING Y P. Preparation of nanoporous material based composite membranes for chemical separations[D]. Beijing:Beijing University of Chemical Technology, 2017.
  [48] LI Y, WU Q X, GUO X H, et al. Laminated self-standing covalent organic framework membrane with uniformly distributed subnanopores for ionic and molecular sieving[J]. Nature Communications, 2020, 11:590.
  [49] ZHAO C, WU B H, MA M Q, et al. Ultrathin metal/covalent-organic framework membranes towards ultimate separation[J]. Chemical Society Reviews, 2019, 48:3811-3841.
  [50] DEY K, PAL M, ROUT K C, et al. Selective molecular separation by interfacially crystallized covalent organic framework thin films[J]. Journal of the American Chemistry Society, 2017, 139:13083-13091.
  [51] HAO Q, ZHAO C Q, SUN B, et al. Confined synthesis of two-dimensional covalent organic framework thin films within superspreading water layer[J]. Journal of the American Chemistry Society, 2018, 140:12152-12158.
  [52] CORCOS A R, LEVATO G A, JIANG Z W, et al. Reducing the pore size of covalent organic frameworks in thin-film composite membranes enhances solute rejection[J]. ACS Materials Letters, 2019, 1:440-446.
  [53] SHINDE D B, SHENG G, LI X, et al. Crystalline 2D covalent organic framework membranes for high flux organic solvent nanofiltration[J]. Journal of the American Chemistry Society, 2018, 140:14342-14349.
  [54] WANG R, SHI X S, XIAO A K, et al. Interfacial polymerization of covalent organic frameworks (COFs) on polymeric substrates for molecular separations[J]. Journal of Membrane Science, 2018, 566:197-204.
  [55] WANG T, WU H Y, ZHAO S, et al. Interfacial polymerized and pore-variable covalent organic framework composite membrane for dye separation[J]. Chemical Engineering Journal, 2020, 384:123347.
  [56] WANG M D, GUO W X, JIANG Z Y, et al. Reducing active layer thickness of polyamide composite membranes using a covalent organic framework interlayer in interfacial polymerization[J]. Chinese Journal of Chemical Engineering, 2020, 28(4):1039-1045.
  [57] YUAN S S, ZHANG G, ZHU J Y, et al. Hydrogel assisted interfacial polymerization for advanced nanofiltration membranes[J]. Journal of Materials Chemistry A, 2020, 8:3238-3245.
  [58] WANG R, SHI X S, ZHANG Z, et al. Unidirectional diffusion synthesis of covalent organic frameworks (COFs) on polymeric substrates for dye separation[J]. Journal of Membrane Science, 2019, 586:274-280.
  [59] WANG R, WEI M J, WANG Y. Secondary growth of covalent organic frameworks (COFs) on porous substrates for fast desalination[J]. Journal of Membrane Science, 2020, 604:118090.
  [60] SHEN J L, ZHANG R N, SU Y L, et al. Polydopamine-modulated covalent organic framework membranes for molecular separation[J]. Journal of Materials Chemistry A, 2019, 7:18063-18071.
  [61] MATSUMOTO M, VALENTINO L, STIEHL G M, et al. Lewis-acid-catalyzed interfacial polymerization of covalent organic framework films[J]. Chem, 2018, 4:308-317.
  [62] GADWAL I, SHENG G, THANKAMONY R L, et al. Synthesis of sub-10 nm two-dimensional covalent organic thin film with sharp molecular sieving nanofiltration[J]. ACS Applied Materials & Interfaces, 2018, 10:12295-12299.
  [63] SHINDE D B, CAO L, WONANKE A D, et al. Pore engineering of ultrathin covalent organic framework membranes for organic solvent nanofiltration and molecular sieving[J]. Chemical Science, 2020, 11:5434-5440.
  [64] LU H, WANG C, CHEN J J, et al. A Novel 3D covalent organic framework membrane grown on a porous α-Al₂O₃ substrate under solvothermal conditions[J]. Chemical Communications, 2015, 51:15562-15566.
  [65] FAN H W, GU J H, MENG H, et al. High-flux imine-linked covalent organic framework COF-LZU1 membranes on tubular alumina supports for highly selective dye separation by nanofiltration[J]. Angewandte Chemie International Edition, 2018, 57(15):4083-4087.
  [66] MANCHANDA P, CHISCA S, UPADHYAYA L, et al. Diffusion-induced in situ growth of covalent organic frameworks for composite membranes[J]. Journal of Materials Chemistry A, 2019, 7:25802-25807.
  [67] PAN F S, GUO W X, SU Y L, et al. Direct growth of covalent organic framework nanofiltration membranes on modified porous substrates for dyes separation[J]. Separation and Purification Technology, 2019, 215:582-589.
  [68] KANDAMBETH S, BISWAL B P, CHAUDHARI H D, et al. Selective molecular sieving in self-standing porous covalent-organic-framework membranes[J]. Advanced Materials, 2017, 29:1603945.
  [69] DEY K, KUNJATTU H. S, CHAHANDE A M, et al. Nanoparticle size-fractionation through self-standing porous covalent organic framework films[J]. Angewandte Chemie International Edition, 2018, 59:1161-1165.
  [70] SHI X S, XIAO A K, ZHANG C X, et al. Growing covalent organic frameworks on porous substrates for moleculesieving membranes with pores tunable from ultra- to nanofiltration[J]. Journal of Membrane Science. 2019, 576:116-122.
  [71] ZHANG X K, LI H, WANG J, et al. In-situ grown covalent organic framework nanosheets on graphene for membrane-based dye/salt separation[J]. Journal of Membrane Science. 2019, 581:321-330.
  [72] XIAO A K, ZHANG Z, SHI X S, et al. Enabling covalent organic framework nanofilms for molecular separation:Perforated polymer-assisted transfer[J]. ACS Applied Materials & Interfaces, 2019, 11:44783-44791.
  [73] LIU C Y, JIANG Y Z, NALAPARAJU A, et al. Post-synthesis of a covalent organic framework nanofiltration membrane for highly efficient water treatment[J]. Journal of Materials Chemistry A, 2019, 7:24205-24210.
  [74] LI Y S, CHEN W B, XING G L, et al. New synthetic strategies toward covalent organic frameworks[J]. Chemical Society Review, 2020, 49:2852-2868.
  [75] KUEHL V A, YIN J S, DUONG P H H, et al. A highly ordered nanoporous, two-dimensional covalent organic framework with modifiable pores, and its application in water purification and ion sieving[J]. Journal of the American Chemistry Society, 2018, 140:18200-18207.
  [76] WANG Z F, YU Q, HUANG Y B, et al. PolyCOFs:a new class of freestanding responsive covalent organic framework membranes with high mechanical performance[J]. ACS Central Science, 2019, 5:1352-1359.
  [77] WANG Z F, ZHANG S N, CHEN Y, et al. Covalent organic frameworks for separation applications[J]. Chemical Society Reviews, 2020, 49:708-735.
  [78] YANG H, YANG L X, WANG H J, et al. Covalent organic framework membranes through a mixed-dimensional assembly for molecular separations[J]. Nature Communications, 2019, 10:2101.
  [79] ZHOU W, WEI M J, ZHANG X, et al. Fast desalination by multilayered covalent organic framework (COF) nanosheets[J]. ACS Applied Materials & Interfaces, 2019, 11:16847-16854.
  [80] WEI W, LIU J, JIANG J W. Computational design of 2D covalent-organic framework membranes for organic solvent nanofiltration[J]. ACS Sustainable Chemistry & Engineering, 2019, 7:1734-1744.
  [81] XU F, WEI M J, ZHANG X, et al. Ion rejection in covalent organic frameworks:Revealing the overlooked effect of in-pore transport[J]. ACS Applied Materials & Interfaces, 2019, 11:45246-45255.
  [82] SONG Y, WEI M J, XU F, et al. Transport mechanism of water molecules passing through polyamide/COF mixed matrix membranes[J]. Physical Chemistry Chemical Physics, 2019, 21:26591-26597.